Multifunctional alcohols obtained from cardanol, multifunctional acrylic crosslinker and pendant phosphorous flame retardant derivatives thereof

ABSTRACT

Multifunctional alcohols, polyols derived from cardanol containing at least 3 hydroxyl groups are disclosed. Such alcohols allow for synthesis of multifunctional crosslinkers such as acrylates, epoxies, and vinyl ethers and flame retardants such as &gt;phosphates. The multifunctional alcohols or polyols can be used in polyurethanes and polycarbonates. The multifunctional crosslinkers can be used in optical coating and waveguide compositions to increase curing speed and crosslink density. The multifunctional phosphates can be used in flame resistant plastics as the highly pendant phosphorus containing phosphate non-halogen flame retardant additives.

This Application is a National Phase Application of InternationalApplication No. PCT/IN2005/000458 filed Dec. 30, 2005.

FIELD OF THE INVENTION

The invention is directed to a class of multifunctional long chainalcohols or polyols containing substituted or unsubstituted aryl unitderived from cardanol which is a byproduct of cashew nut processingindustry and their derivatives such as acrylates and methacrylatescollectively referred to herein as acrylates, and phosphates andpolyphosphates collectively referred to herein as phosphates, epoxiesand vinyl ethers. The acrylates, epoxies and vinyl ethers are used ascrosslinkers in compositions for optical coatings and waveguide devices.Prior art references have disclosed that multifunctional acrylatepolymers may be used for coating applications.

BACKGROUND OF THE INVENTION

Cardanol is a meta-alkene substituted aromatic phenol extracted fromcashew nut shell liquid hereinafter referred as CNSL exudates ofAnacardium occidentale L and a byproduct of cashew processing industry.A number of published literatures are on the derivatisation and use ofcardanol in polymerization and in polyurethanes and epoxies.

Modifications of cardanol and its uses have been widely reported. See,for example, the U.S. Pat. No. 6,723,765 Autodeposited coating of epoxyand OH groups-containing resin with NCO lower T-crosslinker and higherT-crosslinker; U.S. Pat. No. 6,608,164 Salts of heterocyclic diols ascatalysts for melt polycarbonate, U.S. Pat. No. 6,583,258 Salts oforganic phosphates as catalysts for melt polycarbonate; U.S. Pat. No.6,569,928 Phosphorus-containing fire retardant thermoplastic polyestercomposition; U.S. Pat. No. 6,569,918 Polymer composition for curingnovolac resins; U.S. Pat. No. 6,548,623 Method of polycarbonatepreparation; U.S. Pat. No. 6,548,189 Epoxy adhesive; U.S. Pat. No.6,537,636 Data storage media containing clear polycarbonate blends; U.S.Pat. No. 6,525,112 Autodepositable prepolymer of epoxy- andOH-containing resin and hybrid isocyanate crosslinker; U.S. Pat. No.6,451,957 (Hydroxyalkyl)phenols, method for their preparation, and usesthereof; U.S. Pat. No. 6,441,123 Vibration damping monolithic polymers;U.S. Pat. No. 6,255,439 1,1-Bis(4-hydroxyphenyl)-3-alkylcyclohexanes,method for their preparation and polycarbonates prepared there from; andU.S. Pat. No. 6,229,054 Derivative of cardanol and uses therefore.

Acrylic and phosphate derivatives of cardanol were also exemplified inthe following US patents or publications. U.S. Pat. No. 6,211,262Corrosion resistant, radiation curable coating; U.S. Pat. No. 6,177,537Polycarbonates suitable for use in optical articles; U.S. Pat. No.6,133,404 Polyester and formation process thereof U.S. Pat. Nos.6,060,577; 6,060,539 Room-temperature stable, one-component,thermally-conductive, flexible epoxy adhesives; U.S. Pat. No. 6,001,953Polycarbonates suitable for use in optical articles; U.S. Pat. No.5,993,911 Aqueous coating compositions using polyalkylene glycol dialkylethers and process for multi-layer lacquer coating; U.S. Pat. No.4,751,267 Acrylic polyester high solids coatings, U.S. Pat. No.4,141,871 Aqueous dispersions of polyhydroxy polyether resins as coatingcompositions for metallic substrates.

Cardanol modifications are exemplified in the following publications.JHP Tyman, I E Bruce, Synthesis and characterization of polyethoxylatesurfactants derived from phenolic lipids, Journal of Surfactants andDetergents, 2003, Vol 6, Iss 4, pp 291-297; R Saladino, E Mincione, O AAttanasi, P Filippone, Microencapsulated methyl rhenium trioxide(MTO)/H₂O₂ systems for the oxidation of cardanol derivatives; Pure andApplied Chemistry, 2003, Vol 75, Iss 2-3, pp 265-272; Saladino-R Neri-VMincione-E Marini-S Coletta-M Fiorucci-C Filippone-P, A New andEfficient Synthesis of Ortho-Benzoquinones and Para-Benzoquinones ofCardanol Derivatives by the Catalytic-System methyl rhenium trioxide(MTO)/H₂O₂, Journal of the Chemical Society-Perkin Transactions 1, 2000,Iss 4, pp 581-586; O A Attanasi, G Ciccarella, P Filippone, G Mele, JSpadavecchia, G Vasapollo, Novel Phthalocyanines containing cardanolderivatives, Journal of Porphyrins and Phthalocyanines, 2003, Vol 7, Iss1, pp 52-57; Attanasi-O A Buratti-S Filippone-P, RegioselectiveBromination of Cardanol Derivatives, Organic Preparations and ProceduresInternational 1995, Vol 27, Iss 6, pp 645-650;

Amorati-R Pedulli-G F Valgimigli-L Attanasi-O A Filippone-P Fiorucci-CSaladino-R, Absolute Rate Constants for the Reaction of Peroxyl Radicalswith Cardanol Derivatives, Journal of the Chemical Society-PerkinTransactions 2 2001, Iss 11, pp 2142-2146, Saladino-R Neri-V Mincione-EFilippone-P, Selective Oxidation of Phenol and Anisole Derivatives toQuinones with Hydrogen-Peroxide and Polymer-Supported MethylrheniumTrioxide Systems, Tetrahedron 2002, Vol 58, Iss 42, pp 8493-8500,Tagliatesta-P Crestini-C Saladino-R Neri-V Filippone-P Fiorucci-CAttanasi-O A, Manganese and Iron Tetraphenylporphyrin-CatalyzedOxidation of a Cardanol Derivative (Hydrogenated tert-Butylcardanol),Journal of Porphyrins and Phthalocyanines 2002, Vol 6, Iss 1, pp 12-16.

Short-E L, Tychopoulos-V, Tyman-J H P, Long-Chain Phenols-30. A RateStudy of the Mannich Reaction of Phenols (with Particular Reference to3-Pentadecylphenol), Journal of Chemical Technology and Biotechnology1992, Vol 53, Iss 4, pp 389-396, John-G, Pillai-C K S,Self-Cross-Linkable Monomer from Cardanol—Cross-Linked Beads ofPoly(Cardanyl Acrylate) by Suspension Polymerization, MakromolekulareChemie-Rapid Communications 1992, Vol 13, Iss 5, pp 255-259; Sreelatha-SRao-T P Narayanan-C S Damodaran-A D, Isopropyl-3-PentadecylphenylPhosphoric-Acid-A New Reagent for Liquid-Liquid-Extraction andSeparation of Rare-Earths, analytical letters 1993, Vol 26, Iss 3, pp573-591, Bezerra-M Z B Machado-M I L Demorais-S M Braz-R, Synthesis ofNeoflavonoids-4-(4′-Methoxyphenyl)3,4-Dihydrocoumarins, Journal of theBrazilian Chemical Society 1997, vol 8, iss 3, pp 229-234; Roth-MGutsche-B Herderich-M Humpf-H U Schreier-P, Dioxygenation of Long-ChainAlkadien(Trien)ylphenols by Soybean Lipoxygenase, Journal ofAgricultural and Food Chemistry 1998, Vol 46, Iss 8, pp 2951-2956,Deavellar-I G J Godoy-K Demagalhaes-G C, Quaternary Ammonium-SaltsDerived from Cardanol and Their Use as Phase-Transfer Catalyst, Journalof the Brazilian Chemical Society 2000, Vol 11, Iss 1, pp 22-26; Ikeda-RTanaka-H Uyama-H Kobayashi-S A New Cross-Linkable Polyphenol from aRenewable Resource Macromolecular Rapid Communications 2000, Vol 21, Iss8, pp 496-499; Graham-M B Tyman-J H P, Ozonization of Phenols fromAnacardium-Occidentale (Cashew), Journal of the American Oil ChemistsSociety 2002, Vol 79, Iss 7, pp 725-732.

Investigations on Composition and bioactivity of cardanol were reportedin the following examples. Phenolic Lipid-Composition During Developmentof Cashew, Phytochemistry 1992, Vol 31, Iss 7, pp 2295-2297; Bolton-RDemorais-S M, Biologically-Active Derivatives of Cardanol—Antifungal8-Aryloctanoic Acids, Natural Product Letters 1994, Vol 4, Iss 3, pp227-233; Shobha-S V, Ramadoss-C S, Ravindranath-B, Inhibition of SoybeanLipoxygenase-1 by Anacardic Acids, Cardols and Cardanols, Journal ofNatural Products-Lloydia 1994, Vol 57, Iss 12, pp 1755-1757, Lee-J SCho-Y S Park-F J Kim-J Oh-W K Lee-H S Ahn-J S, Phospholipase C-Gamma-1Inhibitory Principles from the Sarcotestas of Ginkgo-Biloba, Journal ofNatural Products 1998, Vol 61, Iss 7, pp 867-871,

Synthesis of advanced materials including Liquid crystalline polymerswere also reported from cardanol as exemplified in the followingpublications. Abraham-S Prasad-V S Pillai-C Ravindranathan-M,Copolyesters of Hydroxyphenylalkanoic Acids-Synthesis andThermal-Properties ofPoly((4-Oxybenzoate)—Co—(8-(3-Oxyphenyl)Octanoate)) andPoly((3-Bromo-4-Oxybenzoate)—Co—(8-(3-Oxyphenyl)Octanoate)), PolymerInternational 2002, Vol 51, Iss 6, pp 475-480; Pillai-C K SSherrington-D C Sneddon-A, Thermotropic Liquid-Crystalline CopolyesterBased on 8-(3-Hydroxyphenyl) Octanoic-Acid and Para-Hydroxybenzoic Acid,Polymer 1992, Vol 33, Iss 18, pp 3968-3970; Saminathan-M Krishna-CPillai-S Pavithran-C, Synthesis and Characterization of Main-ChainLiquid-Crystalline Polymers Containing a P-Phenyleneazo Group,Macromolecules 1993, Vol 26, Iss 25, pp 7103-7105; Liquid-CrystallinePolymers—The Effects of Chain Disrupters, Pure and Applied Chemistry1998, Vol 70, Iss 6, pp 1249-1252, Saminathan-M Pillai-C K S, Synthesisof Novel Liquid-Crystalline Polymers with Cross-Linked NetworkStructures, Polymer 2000, Vol 41, Iss 8, pp 3103-3108,

Synthesis of aryl acrylates based on cardanol were reported in thefollowing publications. John-G Pillai-C K S, Synthesis andCharacterization of a Self-Cross-Linkable Polymer fromCardanol—Autooxidation of Poly(Cardanyl Acrylate) to Cross-Linked Film,Journal of Polymer Science Part A-Polymer Chemistry 1993, Vol 31, Iss 4,pp 1069-1073, Nguyen-L H, Koerner-H Lederer-K, Cure Kinetics of theCardanyl Acrylate-Styrene System Using Isothermal Differential ScanningCalorimetry, Journal of Applied Polymer Science 2002, Vol 85, Iss 9, pp2034-2.

Flame retardant applications of Phosphorylated CNSL system wereexemplified in the following publications. Prasad-V S Pillai-C K S,Flame Retardation of Polyethylene—Effect of a Phosphorus Flame-RetardantHaving Both Hydrophobic and Hydrophilic Groups in the Same Molecule,Journal of Applied Polymer Science 2000, Vol 77, Iss 12, pp 2631-2640;Antony-R, Synthesis, Characterization, and Thermal Studies ofCardanol-Based Polyphosphate Esters, Journal of Polymer Science PartA-Polymer Chemistry 1993, Vol 31, Iss 13, pp 3187-3191, Pillai-C K SPrasad-V S Menon-A R R Sudha-J D Jayakumari-V G Kumar-M B Pavithran-CTikku-V K Pradhan-N K, A Comparative-Evaluation of a NovelFlame-Retardant, 3-(Tetrabromopentadecyl)-2,4,6-Tribromophenol (TBPTP)with Decabromodiphenyloxide (DBDPO) for Applications in LDPE-Based andEVA-Based Cable Materials, Journal of Applied Polymer Science 1997, Vol66, Iss 11, pp 2157-2173.

Polymerisation of modified cardanol and its applications wereexemplified in the following publications. Manjula-S, Kumar-V G,Pillai-C K S, Kinetics and Mechanism of Oligomerization of CardanolUsing Acid Catalysts, Journal of Applied Polymer Science 1992, Vol 45,Iss 2, pp 309-315; Shobha-S V, Krishnaswamy-P R, Ravindranath-B,Antony-R, Pillai-C K S, Synthesis and Thermal Characterization ofChemically-Modified Cardanol Polymers, Journal of Applied PolymerScience 1993, Vol 49, Iss 12, pp 2129-2135; Agrawal-J P, Satpute-R S,Cardanol-Based Epoxy Flexibilizers for Inhibition of CompositePropellants, Journal of Macromolecular Science-Pure and AppliedChemistry 1993, Vol A30, Iss 1, pp 19-34, Swain-S K Sahoo-S Mohapatra-DK Mishra-B K Lenka-S Nayak-P L, Polymers from Renewable Resources-5.Synthesis and Characterization of Thermosetting Resins Derived fromCashew Nut Shell Liquid (CNSL)-Furfural-Substituted Aromatic-Compounds,Journal of Applied Polymer Science 1994, Vol 54, Iss 10, pp 1413-1421,Antony-R Pillai-C K S, Synthesis and Thermal Characterization ofChemically-Modified Phenolic Resins, Journal of Applied Polymer Science1994, Vol 54, Iss 4, pp 429-438, Menon-A R R Pillai-C K S Nando-G B,Chemical Cross-Link Density and Network Structure of Natural-RubberVulcanizates Modified with Phosphorylated Cardanol Prepolymer, Journalof Applied Polymer Science 1994, Vol 51, Iss 13, pp 2157-2164, Sahoo-S KSwain-S K Mohapatra-D K Nayak-P L Lenka-S, Polymers from RenewableResources-6: Synthesis and Characterization of Thermosetting ResinsDerived from Cashewnut Shell Liquid Formaldehyde SubstitutedAromatic-Compounds, Angewandte Makromolekulare Chemie 1995, Vol 233, IssNOV, pp 1-13, Mishra-D K Parida-D Nayak-S S Lenka-S Nayak-P L, Polymersfrom Renewable Resources 0.10. Semiinterpenetrating Polymer NetworksBased on Castor-Oil Polyurethane and Cardanol-Furfural Resin—ScanningElectron-Microscopy and XRD Studies, Journal of MacromolecularScience-Pure and Applied Chemistry 1995, Vol A32, Iss S4, Suppl 4, pp499-510, Nayak-S S Mishra-D K Nayak-P L Lenka-S, Polymers from RenewableResources 0.11. Synthesis and Characterization of Thermosetting ResinsDerived from Cardanyl Acrylate Formaldehyde-SubstitutedAromatic-Compounds, Journal of Macromolecular Science-Pure and AppliedChemistry 1995, Vol A32, Iss S4, Suppl 4, pp 511-521, Nair-CPR Bindu-R LJoseph-V C, Cyanate Esters Based on CardanolModified-Phenol-Formaldehyde Resins—Syntheses andThermal-Characteristics, Journal of Polymer Science Part a-PolymerChemistry 1995, Vol 33, Iss 4, pp 621-627, Tan-T T M,Cardanol-Lignin-Based Epoxy-Resins—Synthesis and Characterization,Journal of Polymer Materials 1996, Vol 13, Iss 3, pp 195-199, Tan-T T M,Cardanol-Lignin-Based Polyurethanes, Polymer International 1996, Vol 41,Iss 1, pp 13-16, Mishra-D K Mishra-B K Lenka-S Nayak-P L, Polymers fromRenewable Resources 0.7. Thermal-Properties of the SemiinterpenetratingPolymer Networks Composed of Castor-Oil Polyurethanes andCardanol-Furfural Resin, Polymer Engineering and Science 1996, Vol 36,Iss 8, pp 1047-1051.

Mohapatra-D K, Nayak-P L, Lenka-S, Polymers from Renewable Resources-21Semiinterpenetrating Polymer Networks Based onCardanol-Formaldehyde-Substituted Aromatic-Compounds CopolymerizedResins and Castor-Oil Polyurethanes—Synthesis, Structure, ScanningElectron-Microscopy and XRD, Journal of Polymer Science Part A-PolymerChemistry 1997, Vol 35, Iss 15, pp 3117-3124,Cardanol-Phenol-Formaldehyde Resins—Thermal-Analysis andCharacterization, Angewandte Makromolekulare Chemie 1996, Vol 243, IssDEC, pp 77-85, Tan-T T M, Cardanol-Glycols and Cardanol-Glycol-BasedPolyurethane Films, Journal of Applied Polymer Science 1997, Vol 65, Iss3, pp 507-510, Thien-D T Vankhoi-N Khang-D Q Vanluyen-D, modification ofrubber by cardanol-formaldehyde resins and epoxidized cardanol, journalof macromolecular science-pure and applied chemistry 1996, Vol A33, Iss12, pp 1963-1972, Tan-T T M, Thermoplastic Composites Based on JuteFiber Treated with Cardanol-Formaldehyde, Polymers & Polymer Composites1997, Vol 5, Iss 4, pp 273-279, Das-T K Das-D Guru-B N Das-K N Lenka-S,Polymers from Renewable Resources—Xxviii—Synthesis, Characterization,and Thermal Studies of Semiinterpenetrating Polymer Networks Derivedfrom Castor-Oil-Based Polyurethanes and Cardanol DerivativesPolymer-Plastics Technology and Engineering 1998, Vol 37, Iss 4, pp427-435, Lin-J H Hu-B H, Study on the Cardanol-Aldehyde CondensationPolymer Containing Boron-Nitrogen Coordinate Bond, Chinese Journal ofPolymer Science 1998, Vol 16, Iss 3, pp 219-225, Bhunia-H P Jana-R NBasak-A Lenka-S Nando-G B, Synthesis of Polyurethane from Cashew NutShell Liquid, a Renewable Resource, Journal of Polymer Science PartA-polymer Chemistry 1998, Vol 36, Iss 3, pp 391-400.

Nair-C P R Bindu-R L Ninan-K N, Recent Advances in Phenolic Resins,Metals Materials and Processes 1997, Vol 9, Iss 2, pp 179-200; Uyama-HKohayashi-S: Enzymatic Polymerization Yields Useful Polyphenols,Chemtech 1999, Vol 29, Iss 10, pp 22-28, Bhunia-H P Nando-G B Basak-ALenka-S Nayak-P L, Synthesis and Characterization of Polymers fromCashewnut Shell Liquid, a Renewable Resource III—Synthesis of aPolyether, European Polymer Journal 1999, Vol 35, Iss 9, pp 1713-1722,Bhunia-H P Nando-G B Chaki-T K Basak-A Lenka-S Nayak-P L, Synthesis andCharacterization of Polymers from Cashewnut Shell Liquid, a RenewableResource II—Synthesis of Polyurethanes, European Polymer Journal 1999,Vol 35, Iss 8, pp 1381-1391; Moreira-L F B Lucas-E F Gonzalez-G,Stabilization of Asphaltenes by Phenolic-Compounds Extracted fromCashew-Nut Shell Liquid, Journal of Applied Polymer Science 1999, Vol73, Iss 1, pp 29-34, Guru-B N Das-T K Lenka-S,N, Polymers from RenewableResources—Xxvii—Studies on Synthesis, Characterization, andThermal-Properties of Resins Derived from CardanylAcrylate-Furfural-Organic Compounds, Polymer-Plastics Technology andEngineering 1999, Vol 38, Iss 1, pp 179-187, Swain-J R Biswal-S KLenka-S, Polymer from Renewable Resources—Studies on Synthesis,Characterization, and Thermal-Properties of Resins Derived fromDiazotized Cardanol-Formaldehyde-Organic Compounds, Polymer-PlasticsTechnology and Engineering 2000, Vol 39, Iss 5, pp 927-936, Bhunia-H PBasak-A Chaki-T K Nando-G B, Synthesis and Characterization of Polymersfrom Cashewnut Shell Liquid—A Renewable Resource V—Synthesis ofCopolyester; European Polymer Journal 2000, Vol 36, Iss 6, pp 1157-1165,Mhaske-S B Bhingarkar-R V Sabne-M B Mercier-R Vernekar-S P, Synthesisand Characterization of End-Capped Polyimides and Their Gas-PermeabilityProperties; Journal of Applied Polymer Science 2000, Vol 77, Iss 3, pp627-635, Ikeda-R Tanaka-H Uyama-H Kobayashi-S Enzymatic-Synthesis andCuring of Poly(Cardanol) Polymer Journal 2000, Vol 32, Iss 7, pp589-593; Paul-R K Pillai-C K S, Melt/Solution Processable ConductingPolyaniline with Novel Sulfonic-Acid Dopants and Its ThermoplasticBlends, Synthetic Metals 2000, Vol 114, Iss 1, pp 27-35; Lubi-M C,Thachil-E T, Cashew Nut Shell Liquid—A Versatile Monomer for PolymerSynthesis, Designed Monomers and Polymers 2000, Vol 3, Iss 2, pp123-153.

Coatings based on CNSL were exemplified in the following publications.Kobayashi-S Uyama-H Ikeda-R Artificial Urushi, Chemistry-A EuropeanJournal 2001, Vol 7, Iss 22, pp 4755-4760, Ikeda-R Tsujimoto-T Tanaka-HOyabu-H Uyama-H Kobayashi-S Man-Made Urushi—Preparation of Cross-LinkedPolymeric Films from Renewable Resources via Air-Oxidation Processes,Proceedings of the Japan Academy Series B-Physical and BiologicalSciences 2000, Vol 76, Iss 10, pp 155-160.

Ikeda-R Tanka-H Uyama-H Kobayashi-S, Synthesis and Curing Behaviors of aCross-Linkable Polymer from Cashew Nut Shell Liquid, Polymer 2002, Vol43, Iss 12, pp 3475-3481; Pillot-J P Birot-M Dao-T M Vu-M D Hoang-N L TTran-T S, The Use of Naturally-Occurring Phenols in the Synthesis ofNovel Functional Polysiloxanes, Surface Coatings International PartB-Coatings Transactions 2001, Vol 84, Iss 3, pp 197-204. There is noreported literature on the highly hydroxylated cardanol derivatives.

It is important to explore and review the use of renewable resourcebased FR additives for plastics which may be cost effective. Pillai etal. and Prasad et al. reported on synthesis of novel phosphorus FRs, andproperties of monophosphorylated product of cardanol which is arenewable resource and a byproduct of cashew industry. They have shownthat the phosphorylated CNSL is an effective non-halogen polymeric flameretardant for plastics and elastomers which will not leech out or bloomfrom the products. The phosphorus content in PCNSL is only 7.9%. It isknown that with the increase in P content the flammability can bebetter. Cardanol can be further functionalized by hydroxylation andphosphorylated for getting higher P content to be a more effective flameretardant. A series of polyphosphates were prepared from derivatives ofcardanol-phosphorodichloridates and dihydric phenols such ashydroquinone, bisphenol, tetrabromobisphenol and phenolphthalein byinterfacial polycondensation (S. Zhang, A. R. Horrocks, Prog. Polym.Sci. 28, 11, 2003, 1517-1538).

There is a strong demand for non-halogen flame retardants for plasticsespecially in the consumer and construction fields due to safetyconcerns associated with higher toxic fumes and related casualties inthe case of fire associated with plastic building materials withbrominated flame retardants. In this context inorganic fillers likehydrated alumina, talc etc. are effective but at the cost of mechanicalproperties of the product.

Most acrylates disclosed in the prior art contain one or two acrylategroups per molecule. However, to achieve fast cure and high crosslinkingdensity it is desirable that multifunctional cross-linkers having atleast 3 functional groups per molecule are added to the formulations.Multifunctional hydrocarbon monomers such as acrylates, vinyl ethers andepoxies have been widely used as cross-linkers but their poor solubilityand low boiling point limits their applications in low volatile organiccoatings. High shrinkage is another disadvantage of aliphatic acrylatebased coatings compared to aliphatic commercial acrylates. Ausimont USAof Thorofare N.J. provides Fluorolink T and T10, which have fourhydroxyl groups per molecule. It is well known to those skilled in theart, due to steric hindrance, it is very difficult to fully convert thesecondary hydroxyl groups to other functional groups such as acrylates,epoxies, and vinyl ethers, especially in the presence of primaryhydroxyl groups. Incomplete conversion of hydroxyl groups makes it lesssuitable for applications requiring low moisture uptake and low opticalabsorption in the 1300-1600 nm wavelength regions.

U.S. Pat. No. 6,229,054 of Cardolite Corporation are on the preparationof derivatives of cardanol and CNSL and U.S. Pat. No. 6,451,957 dealswith the process for the preparation of 8-(3-hydroxyphenyl)octanol fromcardanol.

It is well known in the art that actinic radiation such as UV lightpermits fast curing. UV curable compositions containing multifunctionalacrylates, oligomers and polymers have been widely reported. See, forexample, Chem. Eng. News 2001, Nov. 5, K. D. Weiss, Prog. Polym. Sci.Vol. 22, 203-245, 1997. U.S. Pat. Nos. 4,508,916; 4,511,209; 4,914,171;5,024,507; 5,062,680; 5,223,593; 5,822,489; 6,133,472; European patentNo. 333,464A1; and publications including J. Pacansky, Progress inOrganic Coatings, 18, 1990, 79 and R. Bongiovanni, Progress in OrganicCoatings, 36 (1999) 70; all of which are herein incorporated byreference. These compositions comprise fluorinated mono- ormulti-functional acrylates or vinyl ethers and at least one photoinitiator.

It is well known that Phosphates are used as non-halogen flameretardants especially in plastics which will act in the condensed phaseas well as in the vapour phase for effective flame retardation. See forexample U.S. Pat. Nos. 6,569,928, 3,697,499, 4,010,144, 4,070,336,4,073,767, 4,105,825, 4,073,829, 6,630,565, 5,650,531, 6,733,698 andpublications including S. Zhang, A. R. Horrocks, Prog. Polym. Sci. 28,11, 2003, 1517-1538, S-Y Lu, I. Hamerton Prog. Polym. Sci. 27, 2002,1661-1712. U.S. Pat. No. 6,569,928 comprise phosphorylated flameretardants used in plastics. New methodologies for the Phosphorylationof alcohols including phenols were reported in J. K. Stowell, T. S.Widlanski, Tetrahedron Lett. 36, 11, 1995, 1825-1826.

Therefore there is no reported literature on the derivatisation ofcardanol or Cashew nut shell liquid to a multifunctional alcohol whichare more cost effective, having higher boiling and thermal propertiesand having at least 3 and upto 6 alcohol groups per molecule on theirmixture.

OBJECTS OF THE INVENTION

The main object of the invention is to provide a process for thepreparation of highly hydroxylated cardanol derivative with atleast 3hydroxyl groups including atleast two hydroxyl groups in the side chainwhich can be used in the preparation of polyurethanes, polycarbonatesepoxies etc.

Another object of the invention is to provide a process for thepreparation of a multifunctional alcohol or polyol from cardanol whichis soluble in polar solvents including water.

It is a further object of the invention to provide a process for thepreparation of a multi functional acrylate from the said derivativewhich can be used as a renewable resource based low cost low boilingcross-linker in UV curable or photo curable other acrylic coatingformulations including low volatile organic content coatings.

Another object of the invention is to provide a process for thepreparation of highly pendent phosphorous containing cardanol derivativewith atleast three phosphorus atoms per molecule which can be used as aphosphorus additive in flame retardant formulations.

A further object of the invention is to provide a process for thepreparation of an amphiphilic surfactant molecule from cardanol.

Yet another object of the invention is to provide a process for thepreparation of a multifunctional acrylate which will cure >125 secondsunder Ultra Violet (UV)-radiation.

A further object of the invention is to provide a process for thepreparation of a multifunctional phosphate flame retardant on curingwith aldehydes will show a limiting oxygen index (LOI) value >35.

SUMMARY OF THE INVENTION

The present invention relates to the synthesis of a multifunctionalacrylate or methacrylate containing aryl group as a multifunctionalcrosslinking agent for acrylic polymers especially paints and coatings.

The present invention also relates to the synthesis of a non-halogenflame retardant monomer or oligomer containing highly pendant phosphorusmoieties. In particular, it relates to a process for preparing the flameretardant phosphorus-containing compound through an esterificationreaction.

Multifunctional alcohols and their acrylate and phosphate derivativesprepared by the process of the present invention have the structuregiven below.

Accordingly, the present invention provides a process for thepreparation of multifunctional alcohols or its acrylates or phosphatesderived from cashew nut shell liquid, cardanol or its components of thegeneral formula given above, comprising of the steps of acetylation ofcardanol using acetic anhydride in presence of catalysts such asp-toluene sulphonic acid, benzene sulphonic acid and sulphuric acid attemperature in the range of 30-80° C. for 2-4 h.

In another embodiment of the finding the solvent used for acetylation ofcardanol is selected from N,N-dimethyl formamide, dimethyl sulphoxide,methanol, tetrahydrofuran and acetone.

In another embodiment of the present invention, the acid anhydride usedin the acetyaltion step is selected from the group consisting ofphthalic anhydride, trifluoroacetic anhydride, acetic anhydride andchloroacetic anhydride.

In a further embodiment of the invention, the metal oxide used in thestep of transhydroxylation is selected from the group comprising of,Magnesium Oxide, Nickel oxide, Tungsten oxide, Rhenium Trioxide andTitanium oxide.

In another embodiment of the present invention, the temperature used fortranshydroxylation ranges between 50-140° C.

In another embodiment of the present invention, the time oftranshydroxylation ranges between 2-12 hrs.

In another embodiment of the finding the acryloylation ormethacryloylation of the hydroxylated derivative of cardanol or CNSL iscarried out in presence of acryloyl chloride, methacryloyl chloride and2-ethylhexylacryloyl chloride.

In another embodiment of the finding the temperature of acryloylation is30-45° C.

In another embodiment of the finding the catalyst used in acryloylationis amines selected from methyl amine, triethyl amine, trimethyl amineand diethylamine.

In another embodiment of the finding, phosphorylation of thehydroxylated cardanol was carried out using phosphorylating agentsselected from phosphorus pentoxide, phosphoric acid,phosphorodichloridate and diethyl phosphite.

In another embodiment of the present invention, the acrylate has curedwithin 120 seconds under UV lamp.

In another embodiment of the present invention, the phosphate derivativeshows a Limiting Oxygen Index value above 35.

The main finding underlying the present invention is our observationthat a process for the preparation of hydroxylated cardanol and itsderivatives where one of the hydroxylated products is water soluble withhydroxyl value of >1500 mg of KOH. The acryloylated derivative showedcomplete curing under UV lamp below 120 seconds under a mylar sheet. Thephosphorylated derivative of the above showed a Limiting Oxygen Indexof >35 under ASTM D2863-76 test conditions and a V-0 rating under UL-94flame tests.

DETAILED DESCRIPTION OF THE INVENTION

The process of the present invention has essentially the followingsteps: acetylation of cardanol or CNSL in presence of excess acidanhydrides selected from propionic anhydride, acetic anhydride andtrifluoroacetic anhydride: and trans-hydroxylation of the acyloxyderivative in presence of hydrogen peroxide or Sodium perborate inpresence of acids selected from acetic acid, formic acid, peracetic acidand performic acid and metal oxides selected from the group comprisingof transition metal oxides or Magnesium Oxide, Nickel oxide, Tungstenoxide, Rhenium Trioxide and Titanium oxide at temperatures of 50-140° C.for 2-6 hrs. This was optionally followed by hydrolysis using alkalisolution and a purification step involving extraction using solventmixtures selected from acetone-methanol, acetone-methyl ethyl ketone andacetone-isopropanol mixture and drying under reduced pressure at 30-60°C. for 1-4 h.

The acryloyl derivative was prepared by acylation using acid chloride atice bath conditions in presence of amines as catalysts, theacryloylation or methacryloylation of the hydroxylated derivative ofcardanol or CNSL is carried out in presence of acryloyl chloride,methacryloyl chloride and 2-ethylhexylacryloyl chloride at a temperatureof −5 to 45° C. in presence of amines selected from methyl amine,triethyl amine, trimethyl amine and diethylamine for a time varies from1-3 h.

The phosphorylated derivative of the hydroxylated cardanol was carriedout using phosphorylating agents selected from phosphorus pentoxide,phosphoric acid, phosphorodichloridate and diethyl phosphate at atemperature of 50-120° C. using solvents selected from N,N-dimethylformamide, dimethyl sulphoxide, methanol, tetrahydrofuran and acetonefor a time of 2-6 h. The purification of the product was done by solventextraction using solvents or mixture of solvents selected fromN,N-dimethyl formamide, dimethyl sulphoxide, methanol, tetrahydrofuran,water and acetone and drying under reduced pressure at 30-60° C. for 1-4h.

The main finding underlying the present invention is our observationthat a process for the preparation of hydroxylated cardanol and itsderivatives where one of the hydroxylated products is water soluble withhydroxyl value of >1500 mg of KOH. The acryloylated derivative showedcomplete curing under UV lamp below 120 seconds under a mylar sheet. Thephosphorylated derivative of the above showed a Limiting Oxygen Indexof >35 under ASTM D2863-76 test conditions and a V-0 rating under UL-94flame tests.

The invention is described in detail in the following examples, whichare provided by way of illustration only and should not be construed tolimit the scope of the invention.

EXAMPLE 1

Synthesis of 1-acetoxy-3-(8,11,14-pentadecatrienyl) benzene: A mixtureof acetic anhydride (0.1 mol, 15 ml) and p-toluenesulphonic acid (PTSA,3.15 mol %, 0.6 g) were taken in a two necked RB flask and doubledistilled cardanol (0.1 mol, 30 g) was added dropwise with stirring overa period of 30 minutes at ambient conditions. The reaction was continuedfor 8-12 h. The product (AC) was washed free of acetic acid and catalystwith water and dried.

EXAMPLE 2

Hydroxylation using peroxide with metal oxide: A mixture of 50% H₂O₂(0.66 mol, 26.5 ml), MgO (0.4 mol %, 0.1 g) and CH₃COOH (25 ml, solvent)were taken in a RB flask fitted with reflux condenser and heated to50-70° C. The product obtained from Example 1 was added drop wise over aperiod of 1 hr. It was kept over night under stirring at ambientconditions. Metal oxide was filtered off and the mixture was washed withexcess of water. It was hydrolysed by 10% NaOH solution and neutralizedby dil. HCl, followed by washing with water and dried as mentioned inexample 1. The yield of the product (HC) obtained was 95%.

EXAMPLE 3

A mixture of 50% H₂O₂ (10.2 ml, 0.15 mol) and 85% formic acid (8.12 ml,0.15 mol) was taken in 100 ml RB flask and acetylated cardanol (0.15mole) was added drop wise with constant stirring in ice-cold. It washyrolysed by dil. NaOH solution and neutralized by dil. HCl. Then it waswashed with water and dried as mentioned earlier. The yield obtained was95%.

EXAMPLE 4

Synthesis of Phosphorylated Derivative: HC (0.1 mol) and DMF (25 ml)were taken in a two-necked RB flask connected with reflux condenser andstirred using magnetic stirrer. To the stirring solution, P₂O₅ (0.022mol, 3.19 g) was added portion wise. It was heated to 60-70° C. for 6hrs. The solvent was removed and it was washed with water. Then it wasdried in an air oven at 60° C. under reduced pressure. (Yield 84%).

EXAMPLE 5

Synthesis of Phosphorylated Derivative: A mixture of anhydrous AICl₃(0.001 mol %) and POCl₃ (0.06 mol, 5.68 ml) in DMF (10 ml) was taken ina two necked RB fitted with a reflux condenser and heated to reflux. HC(0.0067 mol, 2 g) in DMF was added drop wise with stirring over a periodof 30 minutes. AlCl₃ was filtered off and the solvent was separated. Itwas precipitated in acetone.

EXAMPLE 6

Synthesis of Phosphorylated Derivative: I₂ (3.19 g, 0.025 mol) was addedto a solution of diethyl phosphite (2.68 ml, 0.02 mol) in ethyl acetate(5 ml) at 0° C. After 5 min. the clear, solution was allowed to warm to25° C. The above solution was added dropwise over a period of 10-15 mts,to a flask containing HC (1 g, 0.0025 mol) and pyridine (2 ml) in ethylacetate (5 ml) at 0° C. After 10 min. it was washed with aqueous NaHSO₄Solvent was removed and the product was dried. Yield was 60%.

EXAMPLE 7

Phosphorylation using Orthophosphoric acid: 85% ortho phosphoric acid (6ml) in ethyl acetate was taken in a RB flask and HC (5 g, 0.012 mol) inethyl acetate was added drop wise. It was heated to 160° C. for 2 hrswith stirring.

EXAMPLE 8

Acryloylated Derivative of HC: 1.5 g of HC (0.0023 mol was taken in a100 ml R.B. flask. 2.15 g of triethyl amine (0.96 mol) in 1:6 ratio andabout 5 ml of toluene as solvent were added. In a pressure equalizingfunnel, 2.2 g of acryloyl chloride was added in 1:7 ratio (0.012 moles)in 5 ml toluene as solvent. Then acryloyl chloride is added dropwise toallow a controlled reaction. The reaction was kept in an ice bath tocontrol the vigorous reaction. Then the reaction was continued for 5hrs. Separated and Purified by column.

EXAMPLE 9

Methacryloylated Derivative of HC:1.5 g of HC (0.0023 mol was taken in a100 ml R.B. flask. 2.15 g of triethyl amine (0.96 mol) in 1:6 ratio andabout 5 ml of toluene as solvent were added. In a pressure equalizingfunnel, 2.2 g of methacryloyl chloride was added in 1:7 ratio (0.012moles) in 5 ml toluene as solvent. The reaction was kept in an ice bathto control the vigorous reaction. Then the reaction was continued for 5hrs. Separated and Purified by column.

The advantages of the present invention are the following:

The present invention provides a process for the preparation ofhydroxylated cardanol. The acryloylated derivative showed completecuring under UV lamp within 60-120 seconds under a mylar sheet. Thephosphorylated derivative of the above showed a Limiting Oxygen Index of40 under ASTM D2863-76 testing and a V-0 rating under UL-94 flame tests.

1. A multifunctional alcohol, or acrylate or phosphate derivativethereof, having a structure:

wherein: X=each independently —(C(OY)R₆)—(CH(OY)R₆) at terminal positionand —(C(OY)R₆)₂— at linking position Y=each independently H,—C(O)—CR₆═CHR₅ or —P(OR₇)₂O R₁═H, OH, COOH or alkyl R₂═H, OH, COOH orHalogen R₃═H, OH, alkyl, aryl, alkoxy, aryloxy or halogen R₄═H, OH,COOH, alkyl, aryl, or halogen R₅=each independently H, alkyl, alkylester, aryl or halogen R₆=each independently OH, alkyl, aryl or halogenR₇=each independently H, OH, halogen, alkoxy, aryloxy, aryl or alkylester R₈═H, alkyloyl, aryloyl or Y wherein the compound comprises atleast three hydroxyl groups including at least two in the side chain. 2.A process for the preparation of multifunctional alcohol from cardanol,or an acryloylated derivative or phosphorylated derivative thereof,comprising the steps of: acetylating cardanol or a derivative thereof,followed by transhydroxylation of the resulting product, to obtain amultifunctional alcohol, or an acryloylated or phosphorylated derivativethereof, having a formula:

wherein: X=each independently —(C(OY)R₆)—(CH(OY)R₆) at terminal positionand —(C(OY)R₆)₂— at linking position Y=each independently H,—C(O)—CR₆═CHR₅ or —P(OR₇)₂O R₁═H, OH, COOH or alkyl R₂═H, OH, COOH orHalogen R₃═H, OH, alkyl, aryl, alkoxy, aryloxy or halogen R₄═H, OH,COOH, alkyl, aryl or halogen R₅=each independently H, alkyl, alkylester, aryl or halogen R₆=each independently OH, alkyl, aryl or halogenR₇=each independently H, OH, halogen, alkoxy, aryloxy, aryl or alkylester R₈═H, alkyloyl, aryloyl or Y wherein the compound comprises atleast three hydroxyl groups including at least two in the side chain. 3.The process of claim 2 wherein acetylation is carried out using an acidanhydride selected from the group consisting of phthalic anhydride,chloroacetic anhydride, propionic anhydride, acetic anhydride andtrifluoroacetic anhydride.
 4. The process of claim 2 wherein acetylationis carried out in the presence of a solvent selected from the groupconsisting of N,N-dimethylformamide, dimethylsulphoxide, methanol andtetrahydrofuran.
 5. The process of claim 2 wherein acetylation iscarried out using a catalyst selected from the group consisting ofp-toluene sulphonic acid, benzene sulphonic acid and sulphuric acid. 6.The process of claim 2 wherein hydroxylation is carried out in thepresence of a reagent selected from the group consisting of hydrogenperoxide, Sodium perborate, Formic acid, peracetic acid, performic acidor a metal oxide selected from the group consisting of a transitionmetal oxide, Tungsten oxide, Magnesium Oxide and Nickel oxide.
 7. Theprocess of claim 2 wherein the temperature used for thetranshydroxylation is between 30-120° C.
 8. The process of claim 2wherein the time of transhydroxylation ranges between 2-12 hrs.
 9. Theprocess of claim 2 wherein the hydroxylated cardanol is highly watersoluble with hydroxyl value of >1500 mg of KOH.
 10. The process of claim2 wherein phosphorylation of the hydroxylated cardanol is carried outusing a reagent selected from the group consisting of phosphoruspentoxide, phosphoric acid, phosphoro dichloridate and diethylphosphite.
 11. The process of claim 2 wherein acryloylation ormethacryloylation is carried out in presence of acryloyl chloride ormethacryloyl chloride in the presence of a triethyl amine catalyst or abase at a temperature in the range of 0-50° C.
 12. The process of claim2 further comprising a step where the acrylate is cured within 120seconds under UV lamp under a Mylar sheet.
 13. The process of claim 2wherein the phosphorylated derivative has a Limiting Oxygen Index of >35under ASTM D2863-76 testing and a V-0 rating under UL-94 flammabilitytests.